CN115240985A - Solid electrolytic capacitor and method for manufacturing solid electrolytic capacitor - Google Patents
Solid electrolytic capacitor and method for manufacturing solid electrolytic capacitor Download PDFInfo
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- CN115240985A CN115240985A CN202210429987.3A CN202210429987A CN115240985A CN 115240985 A CN115240985 A CN 115240985A CN 202210429987 A CN202210429987 A CN 202210429987A CN 115240985 A CN115240985 A CN 115240985A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/0029—Processes of manufacture
- H01G9/0036—Formation of the solid electrolyte layer
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/15—Solid electrolytic capacitors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/022—Electrolytes; Absorbents
- H01G9/025—Solid electrolytes
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
According to one aspect, a solid electrolytic capacitor includes an anode body made of a valve metal, a dielectric layer formed on the anode body, a solid electrolyte layer formed on the dielectric layer, and a cathode body layer formed on the solid electrolyte layer. The solid electrolyte layer includes a first layer including a first conductive polymer doped with a single-molecule dopant and a second conductive polymer composed of a self-doping type conductive polymer including a plurality of side chains containing a functional group capable of being doped, and a second layer formed on the first layer and including a third conductive polymer doped with a polymer dopant; the first conductive polymer is in contact with a third conductive polymer (second layer).
Description
Technical Field
The present disclosure relates to a solid electrolytic capacitor and a method of manufacturing the solid electrolytic capacitor.
Background
In recent years, solid electrolytic capacitors have been widely used in various fields such as the field of electronic devices. Japanese unexamined patent application publication No. h6-69082 discloses a technique for a solid electrolytic capacitor in which a conductive polymer is used as a solid electrolyte.
The solid electrolytic capacitor disclosed in Japanese unexamined patent application publication No. H6-69082 uses a conductive polymer as a solid electrolyte. For example, the conductive polymer may be formed on the dielectric layer by chemical polymerization. However, when a conductive polymer is formed on the dielectric layer by using chemical polymerization, the dielectric layer may be damaged, and thus, insulation properties thereof may be deteriorated. When the insulation property of the dielectric layer is deteriorated as described above, dielectric breakdown may be caused.
For example, deterioration of the insulation of the dielectric layer can be suppressed by reducing the number of times chemical polymerization is performed. However, when the number of times of performing the chemical polymerization is reduced, the conductivity of the solid electrolyte layer is reduced, leading to a problem that the Equivalent Series Resistance (ESR) of the solid electrolytic capacitor is increased.
Disclosure of Invention
In view of the above problems, an object of the present disclosure is to provide a solid electrolytic capacitor capable of suppressing insulation degradation of a dielectric layer and suppressing an increase in ESR thereof, and a method of manufacturing the solid electrolytic capacitor.
A first exemplary aspect is a solid electrolytic capacitor, including: an anode body made of a valve metal; a dielectric layer formed on the anode body; a solid electrolyte layer formed on the dielectric layer; and a cathode layer formed on the solid electrolyte layer. The solid electrolyte layer includes: a first layer comprising a first conductive polymer doped with a single-molecule dopant and a second conductive polymer composed of a self-doping type conductive polymer comprising a plurality of side chains containing a functional group capable of doping; and a second layer formed on the first layer and comprising a third conductive polymer doped with a polymer dopant, the first conductive polymer being in contact with the third conductive polymer.
Another exemplary aspect is a method of manufacturing a solid electrolytic capacitor, including: forming a dielectric layer on an anode body made of a valve metal; forming a solid electrolyte layer on the dielectric layer; and forming a cathode body layer on the solid electrolyte layer. The forming of the solid electrolyte layer includes: forming a first layer by forming a second conductive polymer composed of a self-doping type conductive polymer after forming a first conductive polymer on the dielectric layer by chemical polymerization; and forming a second layer comprising a third conductive polymer on the first layer by using a suspension comprising a conductive polymer doped with a polymer dopant; when the solid electrolyte layer is formed, the formation of the solid electrolyte layer brings the first conductive polymer into contact with the third conductive polymer.
According to the present disclosure, a solid electrolytic capacitor capable of suppressing insulation deterioration of a dielectric layer and suppressing increase of its ESR, and a method of manufacturing such a solid electrolytic capacitor can be provided.
The above and other objects, features and advantages of the present disclosure will be more fully understood from the detailed description given below and the accompanying drawings, which are given by way of illustration only, and thus should not be taken as limiting the present disclosure.
Drawings
Fig. 1 is a sectional view of a solid electrolytic capacitor according to an embodiment;
fig. 2 is a sectional view showing an example of a solid electrolyte layer included in a solid electrolytic capacitor according to an embodiment;
fig. 3 is a sectional view showing an example of a solid electrolyte layer included in a solid electrolytic capacitor according to an embodiment;
fig. 4 is a sectional view showing an example of a solid electrolyte layer included in a solid electrolytic capacitor according to an embodiment;
fig. 5 is a sectional view showing an example of a solid electrolyte layer included in a solid electrolytic capacitor according to an embodiment;
fig. 6 is a flowchart for explaining a method of manufacturing a solid electrolytic capacitor according to an embodiment; and
fig. 7 is a sectional view of a solid electrolyte layer included in a solid electrolytic capacitor according to a comparative example.
Detailed Description
Embodiments according to the present disclosure will be described below with reference to the accompanying drawings.
Fig. 1 shows a sectional view of a solid electrolytic capacitor according to an embodiment. As shown in fig. 1, the solid electrolytic capacitor 1 according to the present embodiment includes an anode body 11, a dielectric layer 12, a solid electrolyte layer 13, a cathode body layer 16, a conductive adhesive 17, an anode lead 18, an external resin 19, and lead frames 20a and 20b.
The anode body 11 is formed by using a porous valve metal. For example, the anode body 11 may be formed by using at least one substance selected from tantalum (Ta), aluminum (Al), niobium (Nb), titanium (Ti), zirconium (Zr), hafnium (Hf), and tungsten (W), or an alloy using these metals. In particular, the anode body 11 is preferably formed by using at least one substance selected from tantalum (Ta), aluminum (Al), and niobium (Nb), or using an alloy of these metals. The anode 11 is formed by using, for example, a plate-like, foil-like or wire-like valve metal, a sintered body containing fine particles of the valve metal, or a porous valve metal having been subjected to surface enlargement treatment by etching.
A dielectric layer 12 is formed on the surface of the anode body 11. For example, the dielectric layer 12 may be formed by anodic oxidation of the surface of the anode body 11. For example, the surface of the anode body 11 is porous, and the dielectric layer 12 is also formed in the pores of the porous surface. For example, in the case where tantalum is used for the anode body 11, a tantalum oxide film (i.e., the dielectric layer 12) may be formed on the surface of the anode body 11 by anodizing the anode body 11. For example, the thickness of the dielectric layer 12 may be adjusted by changing the voltage of the anodization process.
The solid electrolyte layer 13 is formed on the dielectric layer 12. That is, the solid electrolyte layer 13 is formed so as to be in contact with the entire surface of the dielectric layer 12. Details of the solid electrolyte layer 13 will be described later.
The cathode layer 16 is formed on the solid electrolyte layer 13. The cathode layer 16 may be formed by laminating a carbon layer and a silver layer, for example. Note that the carbon layer and the silver layer are merely examples, and the material constituting the cathode body layer 16 is not limited to any particular material, provided that the material is conductive.
As described above, in the solid electrolytic capacitor 1 according to the present embodiment, the dielectric layer 12, the solid electrolyte layer 13, and the cathode layer 16 are sequentially laminated on the anode body 11. Anode body 11 includes anode lead 18, and anode lead 18 is connected to lead frame 20 a. The anode lead 18 is connected to the lead frame 20a by soldering, for example. The cathode layer 16 is connected to the lead frame 20b by a conductive adhesive 17. In the solid electrolytic capacitor 1 according to the present embodiment, except for portions of the two lead frames 20a and 20b (i.e., only portions of the two lead frames 20a and 20b are exposed to the outside), they are covered with the external resin 19.
Next, details of the solid electrolyte layer 13 included in the solid electrolytic capacitor 1 according to the present embodiment will be described. Fig. 2 is a sectional view of an example of a solid electrolyte layer included in the solid electrolytic capacitor according to the present embodiment, and is an enlarged sectional view of a part of the solid electrolytic capacitor 1 shown in fig. 1, including the dielectric layer 12 and the solid electrolyte layer 13. Note that, in fig. 2, the first conductive polymer 25 and the second conductive polymer 26 constituting the solid electrolyte layer 13 are shown in a schematic manner in order to explain the features of the present disclosure. The same applies to fig. 3 to 5.
As shown in fig. 2, the solid electrolyte layer 13 includes a first layer 21 and a second layer 22. The first layer 21 includes a first conductive polymer (CH) 25 and a second conductive polymer (SD) 26. A conductive polymer doped with a single-molecule dopant may be used for the first conductive polymer 25. For example, at least one selected from polypyrrole, polythiophene, polyaniline, and a derivative thereof may be used for the first conductive polymer 25.
For the second conductive polymer 26, a self-doping type conductive polymer including a plurality of side chains having a functional group capable of being doped may be used. For example, the second conductive polymer 26 is a self-doping type conductive polymer which is composed of polypyrrole, polythiophene, or polyaniline, and includes a plurality of side chains having a functional group capable of being doped. That is, at least one conductive polymer selected from these self-doping type conductive polymers may be used for the second conductive polymer 26.
The second layer 22 is formed on the first layer 21. The second layer 22 includes a third conductive polymer (SL). As the third conductive polymer (hereinafter also referred to as the third conductive polymer 22), a conductive polymer doped with a polymer dopant can be used. For example, at least one selected from polypyrrole, polythiophene, polyaniline, and derivatives thereof doped with a polymer dopant having a sulfonic acid group may be used for the third conductive polymer 22. As the polymer dopant, for example, polysulfonylstyrene, derivatives thereof, or copolymers of polysulfonylstyrene may be used.
The solid electrolytic capacitor 1 according to the present embodiment is formed such that the first conductive polymer 25 is in contact with the third conductive polymer (second layer) 22. Fig. 2 shows an example of the structure of the solid electrolytic capacitor 1 in which the first conductive polymer 25 is in contact with the third conductive polymer (second layer) 22, and the void 27 is partially present at the interface between the first layer 21 and the second layer 22.
In the present embodiment, the first conductive polymer 25 is formed by chemical polymerization. For example, after the first conductive polymer 25 is formed by chemical polymerization, the formed first conductive polymer 25 is washed by a solvent (water, ethanol, or the like), so that residues of unreacted substances and oxidizing agents, and the like can be removed. After washing, the first conductive polymer 25 becomes a porous (sponge-like) substance having a large number of voids therein. Therefore, the bulk density of the first conductive polymer 25 is low, and in this state, the resistance of the first conductive polymer 25 is high.
In the present embodiment, the second conductive polymer 26 is formed after the first conductive polymer 25 is formed. Accordingly, some of the voids of the first conductive polymer 25 may be filled with the second conductive polymer 26, thereby forming the first layer 21 in which the first conductive polymer 25 and the second conductive polymer 26 are bonded to each other. Note that since the second conductive polymer 26 is a self-doping type conductive polymer, the overall density of the first layer 21 can be increased, and the resistance of the first layer 21 can be reduced. In particular, after washing, a large number of voids are present in the first conductive polymer 25, and the second conductive polymer 26 can easily penetrate into the voids of the first conductive polymer 25 (i.e., the voids of the first conductive polymer 25 can be easily filled with the second conductive polymer 26).
In addition, the present embodiment is formed such that the first conductive polymer 25 is in contact with the third conductive polymer (second layer) 22. For example, when the second conductive polymer 26 penetrates into the voids of the first conductive polymer 25 (i.e., the voids of the first conductive polymer 25 are filled with the second conductive polymer 26), the first conductive polymer 25 may be exposed on the surface of the first layer 21 by adjusting the concentration and/or amount of the second conductive polymer 26. By forming the third conductive polymer 22 on the surface of the first layer 21 in this state, the first conductive polymer 25 can be brought into contact with the third conductive polymer (second layer) 22.
For example, after the second conductive polymer 26 is infiltrated into the voids of the first conductive polymer 25 (i.e., the voids of the first conductive polymer 25 are filled with the second conductive polymer 26), the first conductive polymer 25 may be exposed on the surface of the first layer 21 by washing the second conductive polymer 26 with a solvent (water, ethanol, or the like). By forming the third conductive polymer 22 on the surface of the first layer 21 in this state, the first conductive polymer 25 can be brought into contact with the third conductive polymer (second layer) 22.
For example, after the first layer 21 is formed, it may be immersed in a suspension containing a third conductive polymer so that the third conductive polymer 22 may be formed on the surface of the first layer 21.
Further, after the first conductive polymer 25 is formed, it may be immersed in a suspension containing a third conductive polymer, and then the second conductive polymer 26 may be injected into the voids of the first conductive polymer 25. Even in this case, the solid electrolyte layer 13 in which the first conductive polymer 25 and the third conductive polymer (second layer) 22 are in contact with each other can be formed.
Although the first conductive polymer 25 is formed by chemical polymerization, it is preferable that the amount of the first conductive polymer 25 is as small as possible in order to suppress insulation degradation of the dielectric layer 12. For example, the amount of the first conductive polymer 25 may be minimized by adjusting the concentration of the monomer used in the chemical polymerization, the concentration of the oxidizing agent, the number of polymerization times, and/or other factors. In particular, it is preferable to minimize the number of times of chemical polymerization (for example, to reduce the number of times of performing chemical polymerization to one) when forming the first conductive polymer 25.
In the present embodiment, the first conductive polymer 25 may form an island-shaped pattern on the surface of the dielectric layer 12. Specifically, as shown in fig. 3, the first conductive polymer 25 may cover the upper surface (front surface) of the dielectric layer 12 in an island pattern. Note that the island-like pattern means that the first conductive polymer 25 is not uniformly formed on the dielectric layer 12, but is formed on the dielectric layer 12 in a discontinuous manner such that the first conductive polymer 25 does not cover the entire upper surface of the dielectric layer 12.
In the example shown in fig. 3, the second conductive polymer 26 is provided so as to cover (or surround) the periphery of the first conductive polymer 25 formed in an island-like pattern. Further, in the example shown in fig. 3, the voids of the first conductive polymer 25 are filled with the second conductive polymer 26. In fig. 3, the second conductive polymer 26 covering the periphery of the first conductive polymer 25 formed in the island-shaped pattern is denoted by reference numerals 26 _1and 26 _2. Further, portions in which the voids of the first conductive polymer 25 are filled with the second conductive polymer 26 are denoted by reference numerals 28\ u 1 to 28 \ u 3. That is, in portions denoted by reference numerals 28 _1to 28_3, the porous (sponge-like) first conductive polymer 25 is formed in an island-like pattern, and the voids of the porous (sponge-like) first conductive polymer 25 are filled with the second conductive polymer 26. The same applies to the other figures.
Further, although the present embodiment is formed such that the first conductive polymer 25 is in contact with the third conductive polymer (second layer) 22, it may be formed such that the second conductive polymer 26 is in contact with the third conductive polymer (second layer) 22.
That is, although the voids 27 are present in a dispersed manner at the interface of the first layer 21 and the second layer 22 in the structure shown in fig. 2, as shown in fig. 4, the second conductive polymer 26 may be provided in the voids 27 (a portion in which the second conductive polymer 26 is provided in the voids 27 is shown by a dotted line indicated by reference numeral 29).
Similarly, although voids 27 are present in a dispersed manner at the interface between the first layer 21 and the second layer 22 in the structure shown in fig. 3, as shown in fig. 5, a second conductive polymer 26 may be provided in the voids 27 (a portion in which the second conductive polymer 26 is provided in the voids 27 is shown by a broken line indicated by reference numeral 29). As described above, when the second conductive polymer 26 is disposed in the void 27, the density of the first layer 21 can be further increased, and thus the resistance of the first layer 21 can be further reduced.
Next, a method of manufacturing the solid electrolytic capacitor according to the present embodiment will be described.
The method of manufacturing a solid electrolytic capacitor according to the present embodiment includes a step of forming a dielectric layer on an anode body made of a valve metal, a step of forming a solid electrolyte layer on the dielectric layer, and a step of forming a cathode body layer on the solid electrolyte layer. The step of forming the solid electrolyte layer includes: forming a first layer by forming a second conductive polymer composed of a self-doping type conductive polymer after forming a first conductive polymer on the dielectric layer by chemical polymerization; and forming a second layer comprising a third conductive polymer on the first layer by using a suspension comprising a conductive polymer doped with a polymer dopant. Further, the method is characterized in that when the solid electrolyte layer is formed, it is formed so that the first conductive polymer is in contact with the third conductive polymer.
The method of manufacturing the solid electrolytic capacitor according to the present embodiment will be described in detail below.
Fig. 6 is a flowchart illustrating a method of manufacturing a solid electrolytic capacitor according to the present embodiment. A method of manufacturing the solid electrolytic capacitor will be described below with reference to fig. 1 and 2.
As shown in fig. 6, when manufacturing a solid electrolytic capacitor, anode body 11 is first formed (step S1). Valve metals may be used for anode body 11. The valve metal may use the materials described above.
Next, the dielectric layer 12 is formed on the surface of the anode body 11 by anodizing the anode body (valve metal) 11 (step S2). Thereafter, the first layer 21 containing the first conductive polymer 25 and the second conductive polymer 26 is formed on the dielectric layer 12 (step S3).
Specifically, first, the first conductive polymer 25 is formed on the dielectric layer 12. A conductive polymer doped with a monomolecular dopant may be used for the first conductive polymer 25. For example, at least one selected from polypyrrole, polythiophene, polyaniline, and a derivative thereof may be used for the first conductive polymer 25. For example, the first conductive polymer 25 may be formed by chemical polymerization.
As an example, anode body 11 having dielectric layer 12 formed thereon (hereinafter also simply referred to as anode body 11) was immersed in an aqueous solution of iron (III) p-toluenesulfonate, and then dried to remove moisture therefrom, so that an oxidant crystal was formed on dielectric layer 12. Next, the anode body 11 was immersed in an undiluted solution of 3,4-ethylenedioxythiophene and allowed to chemically polymerize with the oxidant crystals. Thereafter, the anode body 11 is washed with water and ethanol so that unreacted substances and oxidant residues are removed therefrom. Through the above-described series of processes, the porous (sponge-like) first conductive polymer 25 can be formed on the surface of the dielectric layer 12. Note that the above-described method of forming the first conductive polymer 25 is only one example, and in the present embodiment, the first conductive polymer 25 may be formed by using other methods.
Next, a second conductive polymer 26 is formed on the dielectric layer 12 in which the first conductive polymer 25 is formed. For the second conductive polymer 26, a self-doping type conductive polymer including a plurality of side chains having a functional group capable of being doped may be used. For example, the second conductive polymer 26 is a self-doping type conductive polymer composed of polypyrrole, polythiophene, or polyaniline and including a plurality of side chains having a functional group capable of being doped. That is, at least one conductive polymer selected from these self-doping type conductive polymers may be used for the second conductive polymer 26.
As an example, anode body 11 having first conductive polymer 25 formed thereon is immersed in a solution containing a material of second conductive polymer 26 and dried at a predetermined temperature for a predetermined time, so that second conductive polymer 26 may be formed. In this process, the voids of the first conductive polymer 25 are filled with the second conductive polymer 26. As for the solution of the material containing the second conductive polymer 26, for example, an aqueous solution containing polyethylene dioxythiophene containing a sulfonic acid group directly bonded to the backbone of the polyethylene dioxythiophene can be used. Note that the above-described method of forming the second conductive polymer 26 is only one example, and in the present embodiment, the second conductive polymer 26 may be formed by using other methods.
Next, the second layer 22 containing the third conductive polymer is formed on the first layer 21 containing the first conductive polymer 25 and the second conductive polymer 26 (step S4). Note that, in the present embodiment, the solid electrolyte layer 13 is formed such that the first conductive polymer 25 is in contact with the third conductive polymer (second layer 22).
A conductive polymer doped with a polymer dopant may be used for the third conductive polymer. For example, at least one selected from polypyrrole, polythiophene, polyaniline, and derivatives thereof doped with a polymer dopant having a sulfonic acid group may be used as the third conductive polymer 22. For the polymer dopant, for example, polysulfonylstyrene, derivatives thereof, or copolymers of polysulfonylstyrene may be used.
As an example, anode body 11 having first layer 21 formed therein as described above is immersed in a suspension containing a third conductive polymer and dried at a predetermined temperature for a predetermined time, so that second layer 22 containing the third conductive polymer may be formed on first layer 21.
Note that the above-described method of forming the second layer 22 is only an example, and in this embodiment, the second layer 22 may be formed by using another method.
After the second layer 22 is formed, the cathode layer 16 is formed (step S5). The cathode body layer 16 may be formed, for example, by laminating a carbon layer and a silver layer.
Next, lead frames (electrodes) 20a and 20b are formed (step S6). Specifically, the lead frame 20a is connected to the anode lead 18 by soldering. Further, the lead frame 20b is connected to the cathode body layer 16 by a conductive adhesive 17.
Thereafter, the external resin 19 is formed (step S7). Note that the external resin 19 is formed so that portions of the two lead frames 20a and 20b are exposed to the outside. The resin used for the external resin 19 is not particularly limited. For example, a thermosetting epoxy resin or a method for curing a liquid resin may be used.
By using the above-described method of manufacturing a solid electrolytic capacitor, a solid electrolytic capacitor according to the present embodiment can be manufactured.
As described in the background section, conductive polymers have been widely used as solid electrolytes for solid electrolytic capacitors. For example, the conductive polymer may be formed on the dielectric layer by chemical polymerization. However, when a conductive polymer is formed on the dielectric layer by chemical polymerization, the dielectric layer may be damaged, and thus insulation thereof may be deteriorated. When the insulation property of the dielectric layer is deteriorated as described above, dielectric breakdown may be caused.
For example, insulation deterioration of the dielectric layer can be suppressed by reducing the number of times chemical polymerization is performed. However, when the number of times of the chemical polymerization to be performed is reduced, the conductivity of the solid electrolyte layer is reduced, resulting in a problem that the Equivalent Series Resistance (ESR) of the solid electrolytic capacitor is increased.
In the present embodiment, the solid electrolyte layer 13 is formed by using the first layer 21 and the second layer 22. In addition, the first layer 21 is formed by using a first conductive polymer 25 doped with a monomolecular dopant and a second conductive polymer 26 composed of a self-doping type conductive polymer including a plurality of side chains having a functional group capable of being doped. In addition, the second layer 22 is formed by using a third conductive polymer doped with a polymer dopant. Note that the solid electrolyte layer is formed such that the first conductive polymer 25 is in contact with the third conductive polymer (second layer 22).
With the above structure, it is possible to minimize the amount of the first conductive polymer 25 (conductive polymer doped with a single-molecule dopant) formed by chemical polymerization while making up for the deficiency of the solid electrolyte by the second conductive polymer 26 composed of a self-doping type conductive polymer. Accordingly, insulation deterioration of the dielectric layer 12 can be suppressed, thereby preventing or reducing a decrease in conductivity of the solid electrolyte layer 13. In addition, in the present embodiment, since the first conductive polymer 25 is in contact with the third conductive polymer (second layer 22), peeling can be suppressed from occurring at the interface between the first layer 21 and the second layer 22. Therefore, an increase in ESR of the solid electrolytic capacitor can be suppressed. Therefore, a solid electrolytic capacitor capable of suppressing insulation deterioration of the dielectric layer and suppressing increase in ESR, and a method of manufacturing such a solid electrolytic capacitor can be provided.
Fig. 7 is a sectional view of a solid electrolyte layer included in a solid electrolytic capacitor according to a comparative example. In the comparative example shown in fig. 7, after forming the conductive polymer layer 125 on the dielectric layer 112 by chemical polymerization, the first layer 121 is formed by forming the self-doping type conductive polymer layer 126 to cover the conductive polymer layer 125. Thereafter, a second layer 122 is formed on the first layer 121 by using a conductive polymer doped with a polymer dopant. The second layer 122 is formed by using a suspension of a conductive polymer. The first layer 121 and the second layer 122 constitute the solid electrolyte layer 113.
In the comparative example shown in fig. 7, the entire surface of the self-doping type conductive polymer layer 126 is in contact with the second layer 122 (conductive polymer doped with polymer dopant). The inventors of the present application found that in such a structure, interfacial peeling occurs at the interface between self-doping type conductive polymer layer 126 and second layer 122, so that the initial ESR of the product and its ESR after the heat resistance test are increased.
Based on the above findings, in the present disclosure, the first conductive polymer 25 doped with a single-molecule dopant is in contact with the third conductive polymer (second layer 22). By adopting such a structure, peeling can be suppressed from occurring at the interface between the first layer 21 and the second layer 22. That is, since the first conductive polymer 25 has a sponge-like structure, it has an uneven surface. By bringing the first conductive polymer 25 having an uneven surface and the third conductive polymer 22 into contact with each other, the third conductive polymer 22 enters gaps (voids) of the first conductive polymer 25. As a result, the adhesive contact between the first conductive polymer 25 and the third conductive polymer 22 is improved, and therefore peeling at the interface between the first layer 21 and the second layer 22 can be suppressed. Therefore, the initial ESR of the solid electrolytic capacitor and the increase in ESR after the heat resistance test thereof can be suppressed.
[ examples ]
The present disclosure will be described in a more specific manner by using examples thereof, but the present disclosure is not limited to these examples.
< example 1>
The sample according to example 1 was manufactured by the following method (see fig. 6).
First, a tantalum powder having a charge-to-mass ratio of 23000 μ FV/g was used to prepare a tantalum sintered body. Specifically, first, tantalum powder in which an anode lead (tantalum wire) is embedded (i.e., embedded) is press-molded. Thereafter, the molded body was sintered at 1500 ℃, thereby producing a tantalum sintered body (anode body).
The anode body was then welded to a special aluminum holder. Then, a dielectric layer (Ta) was formed by immersing the anode body in a phosphoric acid aqueous solution having a liquid temperature of 60 ℃ and a concentration of 0.05wt%, and anodizing it by applying a voltage of 70V for 10 hours 2 O 5 )。
Next, the anode body having the dielectric layer formed thereon (hereinafter simply referred to as an anode body) was immersed in an aqueous solution of iron (III) p-toluenesulfonate having a concentration of 30wt%, and then dried to remove moisture therefrom, so that an oxidant crystal was formed on the dielectric layer. The anode body was then immersed in an undiluted solution of 3,4-ethylenedioxythiophene and allowed to chemically polymerize with the oxidant crystals. Thereafter, the anode body is washed with water and ethanol so that unreacted substances and oxidant residues are removed therefrom. Through the above-described series of processes, the porous (sponge-like) first conductive polymer (CH) is formed on the surface of the dielectric layer.
Next, the anode body on which the first conductive polymer (CH) was formed was immersed in a solution of a material containing the second conductive polymer (SD) and dried at 120 ℃ for 15 minutes, thereby forming the second conductive polymer (SD). For the solution of the material containing the second conductive polymer (SD), an aqueous solution containing 1wt% of polyethylene dioxythiophene containing a sulfonic acid group, in which the sulfonic acid group is directly bonded to the polyethylene dioxythiophene skeleton, was used. In this process, the second conductive polymer (SD) is formed so as to penetrate into the voids of the first conductive polymer (CH).
Next, the anode body on which the first conductive polymer and the second conductive polymer were formed was immersed in a suspension containing a third conductive polymer (SL), and dried at 120 ℃ for 15 minutes, so that the third conductive polymer (second layer) was formed on the first conductive polymer and the second conductive polymer (first layer). The third conductive polymer uses an aqueous dispersion of polyethylene dioxythiophene doped with polystyrene sulfonate.
Next, the anode body on which the third conductive polymer (second layer) is formed is immersed in a solution obtained by dispersing carbon particles and a binder resin in an organic solvent. Then, after the anode body was taken out from the solution, the solvent was removed by heating the anode body, so that a carbon layer was formed thereon. Next, the anode body is immersed in a silver paste obtained by dispersing silver particles and a binder resin in an organic solvent. Then, after the anode body is taken out of the solution, the solvent is removed by heating the anode body so that a silver layer is formed thereon. Thus, a carbon layer and a silver layer are formed on the solid electrolyte layer. Note that a thermosetting resin or a thermoplastic resin may be appropriately selected (i.e., used) as the binder resin.
After the silver layer is formed, the anode lead is soldered to the anode lead frame. In addition, the silver layer and the cathode lead frame are fixed by a conductive adhesive. Thereafter, the solid electrolytic capacitor is manufactured by encapsulating it with an external resin.
< example 2>
In example 2, the second conductive polymer (SD) was prepared by the following method.
That is, the anode body on which the first conductive polymer (CH) is formed is immersed in a solution of a material containing the second conductive polymer (SD) and dried at 120 ℃ for 15 minutes, so that the second conductive polymer (SD) is formed. For the solution of the material containing the second conductive polymer (SD), an aqueous solution containing 2wt% of polyethylene dioxythiophene containing a sulfonic acid group, in which the sulfonic acid group is directly bonded to the backbone of the polyethylene dioxythiophene, was used. In this process, the second conductive polymer (SD) is formed so as to penetrate into the voids of the first conductive polymer (CH).
Thereafter, the excess second conductive polymer (SD) formed on the surface of the first conductive polymer (CH) was removed by washing the anode body with water for 15 minutes and washing it with ethanol for 15 minutes.
The remaining manufacturing method is similar to that in example 1.
< example 3>
In example 3, the first conductive polymer (CH) was produced by the following method.
That is, the anode body having the dielectric layer formed thereon was immersed in an aqueous iron (III) p-toluenesulfonate solution diluted to 10wt%, and then dried to remove moisture therefrom, so that an oxidizer crystal was formed on the dielectric layer. The anode body was then immersed in an undiluted solution of 3,4-ethylenedioxythiophene and allowed to chemically polymerize with the oxidant crystals. Thereafter, the anode body is washed with water and ethanol, so that unreacted substances and oxidizing agent residues are removed therefrom. Through the above-described series of processes, the porous (sponge-like) first conductive polymer (CH) is formed in an island-like pattern on the surface of the dielectric layer.
The remaining manufacturing method is similar to that in example 1.
< example 4>
In example 4, the second conductive polymer (SD) and the third conductive polymer (SL) were prepared by the following methods.
That is, the anode body on which the first conductive polymer (CH) is formed is immersed in a suspension containing the third conductive polymer (SL). In this process, the anode body is dipped in such a way that the suspension does not come into contact with the surface of the anode body under which the anode lead (tantalum wire) is embedded (i.e. embedded). Thereafter, the third conductive polymer (SD) was formed on the first conductive polymer (CH) by drying the anode body at 120 ℃ for 15 minutes.
Thereafter, 1 μ L of a solution of a material containing the second conductive polymer (SD) was injected using a syringe to a surface in which the anode lead was embedded (i.e., a surface in which the first conductive polymer (CH) was not covered with the third conductive polymer (SL)), and dried at 120 ℃ for 15 minutes. As a result, the second conductive polymer (SD) is formed such that the second conductive polymer (SD) spreads over all voids of the first conductive polymer (CH) and the second conductive polymer (SD) is in contact with the third conductive polymer (SL). For the solution of the material containing the second conductive polymer (SD), an aqueous solution containing 2wt% of polyethylene dioxythiophene containing a sulfonic acid group, in which the sulfonic acid group is directly bonded to the backbone of the polyethylene dioxythiophene, was used.
The remaining manufacturing method is similar to that in example 2.
< comparative example 1>
As comparative example 1, a solid electrolytic capacitor including a solid electrolyte layer in which the first conductive polymer (CH) is not in contact with the third conductive polymer (SL) was manufactured (corresponding to the structure shown in fig. 7). Specifically, the number of times the anode body is immersed in a solution of a material containing the second conductive polymer (SD) is increased, so that the second conductive polymer (SD) is formed to completely cover the first conductive polymer (CH). Note that the state in which the second conductive polymer (SD) completely covers the first conductive polymer (CH) is checked (i.e., observed) by using an electron microscope. The remaining manufacturing method is similar to that in example 1.
< evaluation of sample >
The ESR of the solid electrolytic capacitors according to examples 1 to 4 and the solid electrolytic capacitor according to comparative example 1 manufactured as described above was measured by the following procedure.
First, the initial ESR of each sample at a frequency of 100kHz was measured at room temperature by using a four-terminal measurement type LCR meter. Next, as a heat resistance test, a rated voltage was applied to each sample at a temperature of 105 ℃ for 1000 hours. Thereafter, ESR was measured by a method similar to the above method. Table 1 shows the results of the measurement. Note that the initial ESR in table 1 has been normalized so that the initial ESR value of example 1 is 1. For example, example 2 has an initial ESR of 1.02, which means that example 2 has an initial ESR value 1.02 times that of example 1. The same applies to the initial ESR values of examples 3 and 4 and the initial ESR value of comparative example 1. In table 1, the column "ESR change rate after heat resistance test" indicates the change width (= (ESR value after heat resistance test)/(initial ESR value)) from the initial ESR of each sample.
[ Table 1]
| Initial ESR | ESR Change Rate after Heat resistance test | |
| Example 1 | 1 | 1.50 |
| Example 2 | 1.02 | 1.52 |
| Example 3 | 1.05 | 1.45 |
| Example 4 | 0.97 | 1.46 |
| Comparative example 1 | 1.20 | 2.00 |
As shown in table 1, each of examples 1 to 4 had a smaller initial ESR and a smaller ESR change rate after the heat resistance test than comparative example 1. Since the first conductive polymer (CH) has a sponge-like structure, it has an uneven surface. By bringing the first conductive polymer (CH) having an uneven surface and the third conductive polymer (SL) into contact with each other, the third conductive polymer (SL) enters gaps (i.e., voids) in the first conductive polymer (CH). It is known that as a result, the adhesive contact of the first conductive polymer (CH) and the third conductive polymer (SL) is improved, and therefore peeling at the interface between the first layer and the second layer can be suppressed.
In addition, the ESR change ratio after the heat resistance test in example 4 is excellent. The reason for this excellent rate of change may be as follows. That is, by bringing the first conductive polymer (CH) and the third conductive polymer (SL) into contact with each other before the second conductive polymer (SD) is formed, the contact area therebetween can be increased. Further, another credible reason is as follows. That is, since the second conductive polymer (SD) and the third conductive polymer (SL) are in contact with each other in addition to the contact between the first conductive polymer (CH) and the third conductive polymer (SL), a wide conductive path in the solid electrolyte layer can be ensured, thereby also reducing the initial ESR value.
It will be apparent from the disclosure so described that the embodiments of the disclosure may be varied in many ways. Such variations are not to be regarded as a departure from the spirit and scope of the disclosure, and all such modifications as would be obvious to one skilled in the art are intended to be included within the scope of the following claims.
Claims (8)
1. A solid electrolytic capacitor, comprising:
an anode body made of a valve metal;
a dielectric layer formed on the anode body;
a solid electrolyte layer formed on the dielectric layer; and
a cathode layer formed on the solid electrolyte layer, wherein
The solid electrolyte layer includes:
a first layer comprising a first conductive polymer doped with a single-molecule dopant and a second conductive polymer composed of a self-doping type conductive polymer comprising a plurality of side chains containing a functional group capable of being doped; and
a second layer formed on the first layer, the second layer comprising a third conductive polymer doped with a polymer dopant, and
the first conductive polymer is in contact with the third conductive polymer.
2. The solid electrolytic capacitor as claimed in claim 1, wherein the first conductive polymer forms an island-like pattern on the surface of the dielectric layer.
3. The solid electrolytic capacitor as claimed in claim 1 or 2, wherein the second conductive polymer is in contact with the third conductive polymer.
4. The solid electrolytic capacitor as claimed in any one of claims 1 to 3, wherein the first conductive polymer is at least one selected from polypyrrole, polythiophene, polyaniline and derivatives thereof.
5. The solid electrolytic capacitor as claimed in any one of claims 1 to 4, wherein the second conductive polymer is a self-doping type conductive polymer composed of polypyrrole, polythiophene or polyaniline and containing a plurality of side chains having a functional group capable of being doped, and is at least one conductive polymer selected from the self-doping type conductive polymers.
6. The solid electrolytic capacitor as claimed in any one of claims 1 to 5, wherein the third conductive polymer is at least one selected from polypyrrole, polythiophene, polyaniline and derivatives thereof, and is doped with a polymer dopant containing a sulfonic acid group.
7. The solid electrolytic capacitor as claimed in claim 6, wherein the polymer dopant is polysulfonylstyrene, a derivative thereof or a copolymer of polysulfonylstyrene.
8. A method of manufacturing a solid electrolytic capacitor, comprising:
forming a dielectric layer on an anode body made of a valve metal;
forming a solid electrolyte layer on the dielectric layer; and
forming a cathode layer on the solid electrolyte layer, wherein
The forming of the solid electrolyte layer includes:
forming a first layer by forming a second conductive polymer composed of a self-doping type conductive polymer after forming a first conductive polymer on the dielectric layer by chemical polymerization; and
forming a second layer comprising a third conductive polymer on the first layer by using a suspension comprising a conductive polymer doped with a polymer dopant, and
when the solid electrolyte layer is formed, the solid electrolyte layer is formed so that the first conductive polymer is in contact with the third conductive polymer.
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| JPH0669082A (en) | 1992-08-19 | 1994-03-11 | Nec Corp | Manufacture of solid electrolytic capacitor |
| JP3068430B2 (en) * | 1995-04-25 | 2000-07-24 | 富山日本電気株式会社 | Solid electrolytic capacitor and method of manufacturing the same |
| JP4845699B2 (en) * | 2006-12-08 | 2011-12-28 | 三洋電機株式会社 | Solid electrolytic capacitor and method for producing solid electrolytic capacitor |
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| US9959980B2 (en) * | 2014-12-09 | 2018-05-01 | Showa Denko K.K. | Solid electrolytic capacitor element and method for manufacturing solid electrolytic capacitor element |
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